KR100970462B1 - Anticorrosion metal film composition for energy saving and manufacturing method of the same - Google Patents

Abstract

PURPOSE: An anti-corrosive metal coating composition is provided to obtain high energy saving effect by enabling a cold hardening process and to obtain excellent properties including corrosion resistance, chemical resistance, durability, and mechanical strength while preventing a particle of a metal coating film from penetrating into an anti-corrosive coating film. CONSTITUTION: An anti-corrosive metal coating composition capable of saving energy comprises: metal powder which has a particle size of 5-10 microns and is selected from a group comprising aluminum, magnesium, and their alloy; a first sol-gel resin which is selected from a group comprising zirconium tetra-n-butanolate, zirconium butoxide, isopropyl titanate, and their mixture; a second sol-gel resin which is selected from a group comprising tri-(3-(trimethoxysily)propyl)isocyanurate, gamma-methacryloxypropyltrimethoxysilane, n-phenyl-gamma-aminopropyltrimethoxysilane, and their mixture; and a solvent.

Description

Energy-saving anticorrosive metal coating composition and its manufacturing method {Anticorrosion metal film composition for energy saving and manufacturing method of the same}

The present invention relates to an anticorrosive coating agent, and more particularly, to an energy-saving anticorrosive metal coating composition used in an anticorrosive coating agent for forming a composite layer of a metal coating film and an anticorrosive coating film, and a method of manufacturing the same.

Anticorrosive coatings are coatings that coat the object to form a coating and protect the object from contamination or corrosion, especially to protect the outer surfaces of metal parts that are assembled or bonded to various products manufactured in each industry. It is widely used for the purpose.

The anticorrosive coating agent generally comprises a metal powder having a main rust preventing function, an organic solvent, and various additives for imparting special functions such as heat resistance, weather resistance, thermal stability, and rust resistance.

Such anticorrosive coating agents usually form one coating layer, but Korean Patent Publication No. 10-0848671 discloses a method and a composition for forming a metal coating film and an anticorrosive coating film thereon to form two composite coating layers. have.

That is, a method of forming a composite plating layer by forming a metal plating layer on an object, applying a composition for anticorrosive coating on the metal plating layer to form an anticorrosive coating, and curing it at a high temperature of 280 ° C to 350 ° C is disclosed. .

This method is a two-coating 1 baking method, which exhibits superior anticorrosive properties than other conventional anticorrosive coating layers, but has a high curing temperature of 280 to 350 ° C., resulting in high carbon emissions and high energy consumption. There is a problem that the defect rate is high and the acid resistance and the corrosion resistance are degraded.

An object of the present invention is to provide a metal coating composition for anticorrosion that can be cured at a low temperature, high energy saving efficiency during manufacture, and particles of the metal coating do not penetrate the anticorrosive coating.

Metal coating composition according to one aspect of the invention,

At least one metal powder having a particle size of 5 to 10 μm and selected from the group consisting of aluminum, magnesium, and alloys thereof;

A first sol-gel resin selected from the group consisting of zirconium tatra-normal-butanolate, zirconium butoxide, isopropyl titanate, and mixtures thereof;

Tri- (3- (trimethoxysil) propyl) isocyanurate, gamma-methacryloxypropyltrimethoxysilane and normal-phenyl-gamma-aminopropyltrimethoxysilane, and mixtures thereof Second sol-gel resin; And

It is characterized by including a solvent.

At this time, the metal powder is preferably 100 to 160 parts by weight, the first sol gel resin is 35 to 60 parts by weight, the second sol gel resin is 165 to 250 parts by weight, the solvent is preferably composed of 60 to 90 parts by weight.

In addition, the metal powder is preferably made of aluminum magnesium alloy 70 to 100 parts by weight, aluminum 30 to 60 parts by weight.

In addition, the first sol-gel resin is preferably composed of 20 to 30 parts by weight of zirconium tatra-normal-butanolate, 10 to 20 parts by weight of zirconium butoxide and 5 to 10 parts by weight of isopropyl titanate.

In addition, the second sol-gel resin is 30 to 50 parts by weight of tri- (3- (trimethoxysil) propyl) isocyanurate, 50 to 70 parts by weight of gamma-methacryloxypropyltrimethoxysilane and normal-phenyl- It is preferable that it consists of 50-70 weight part of gamma-aminopropyl trimethoxysilane.

In addition, the solvent is preferably acetone.

According to another aspect of the present invention, a method for preparing an energy-saving anticorrosive metal coating composition may include a metal powder selected from the group consisting of aluminum, magnesium, and alloys of 5 to 10 μm in a solvent at room temperature for 2 to 3 hours. Metal powder dispersion step of mixing;

Zirconium tatra-normal-butanolate, zirconium butoxide, isopropyl titanate, and a first sol gel resin selected from the group consisting of the mixture are added to the mixture of the metal powder dispersion step for 300 to 3 hours. Mixing and stirring the first sol-gel resin, which is stirred at 400 rpm; And

Tri- (3- (trimethoxysil) propyl) isocyanurate, gamma-methacryloxypropyltrimethoxysilane and normal-phenyl-gamma-aminopropyltrime in the mixture of the first sol-gel resin mixing and stirring step And a second sol-gel resin mixing and stirring step of adding a second sol-gel resin selected from the group consisting of oxysilane and a mixture thereof and stirring the mixture at 100 to 200 rpm for 4 to 7 hours.

At this time, the temperature of the first sol-gel resin mixing and stirring step is preferably maintained at 15 to 20 ℃.

In addition, the temperature of the second sol-gel resin mixing and stirring step is preferably maintained at 10 to 15 ℃.

The anticorrosive metal coating composition according to the embodiment of the present invention does not penetrate the anticorrosive coating layer formed thereon, and thus has excellent effects such as physical properties such as corrosion resistance, chemical resistance, durability, and mechanical strength.

In addition, the anti-corrosive metal coating composition according to an embodiment of the present invention is capable of curing at low temperatures, thereby reducing energy and reducing environmental pollution.

The anticorrosive metal coating composition according to one aspect of the present invention includes a metal powder, a sol-gel resin and a solvent.

Metal powder uses light metals, such as aluminum, magnesium, and an aluminum-magnesium alloy, as a main material layer for giving the antirust function of an anticorrosive coating agent. At this time, the particle size of the metal powder is preferably 5 to 10㎛, if less than 5 has a problem that the specific surface area is large, the viscosity rises, if it exceeds 10 penetrates the anticorrosive coating film to be formed on the upper metal coating film This is because there is a problem that the acid resistance is lowered.

Metal powders are generally spherical, but if each particle is not perfectly spherical, the particle size is defined as the average of the length of the longest line segment and the length of the shortest line segment that pass through the interior of the particle.

In addition, there are minute differences between the particle sizes inside the powder, but the largest number of particles are distributed or the average particle size is regarded as the particle size of the powder.

The metal powder is preferably contained in 100 to 160 parts by weight. If the metal powder is less than 100 parts by weight, there is a problem that the heat resistance is lowered, and if it exceeds 160 parts by weight, there is a problem that the adhesive strength is reduced.

Sol gel resin refers to a gel resin obtained by the Sol-Gel Reaction. Zirconium Tatra-Normal-Butanolate, Zirconium Butoxide, Isopropyl Titanate, Tri- (3- (trimethoxysilyl) propyl) isocyanurate, Gamma-Methacryloxypropyltrimethoxysilane, Normal-phenyl- At least one or more materials may be used in the group consisting of gamma-aminopropyltrimethoxysilane, and mixtures thereof.

The sol-gel resin has excellent adhesion to the metal powder and the structure is dense so that the constituents of the metal coating film cannot penetrate into the anticorrosive coating film, and are excellent in corrosion resistance, acid resistance, heat resistance and scratch resistance.

The sol-gel resin is preferably contained in an amount of 165 to 250 parts by weight, and more preferably, the sol-gel resin is separated into a first sol-gel resin and a second sol-gel resin, and as a first sol-gel resin, zirconium tatra-normal-butanolate 20 to 30 weight Parts, 10 to 20 parts by weight of zirconium butoxide, and 5 to 10 parts by weight of isopropyl titanate to make the first sol-gel resin as a whole to 35 to 60 parts by weight, and as a second sol-gel resin, tri- (3- (trimethock) Sicily) propyl) isocyanurate 30 to 50 parts by weight, gamma-methacryloxypropyltrimethoxysilane 50 to 70 parts by weight and normal-phenyl-gamma-aminopropyltrimethoxysilane 50 to 70 parts by weight It is preferable to make the resin into 130 to 190 parts by weight.

If the content of zirconium tatra-normal-butanolate, zirconium butoxide and isopropyl titanate as the first sol-gel resin is out of the above-mentioned ranges, fine particles are formed during coating and nozzle clogging occurs when spray coating. As it occurs, the content has an important meaning.

In addition, the content of tri- (3- (trimethoxysil) propyl) isocyanurate, gamma-methacryloxypropyltrimethoxysilane and normal-phenyl-gamma-aminopropyltrimethoxysilane as the second sol-gel resin is If it is out of the range listed in the above, the uniform dispersion of the metal powder is not made because the sedimentation phenomenon is very severe and difficult to use.

Since the sol gel resin is very sensitive and the gelation phenomenon occurs as soon as the stability decreases according to the order or temperature during manufacturing, the sol gel resin is experimentally divided into the first sol gel resin and the second sol gel resin by reflecting the tendency to gel. The resin is mixed and stirred in the order of the second sol-gel resin.

The solvent may be, but not limited to, acetone, dipropylene glycol, butyl diglycol, isopropyl alcohol, and the like, and acetone may be more preferably used.

Meanwhile, the anticorrosive metal coating composition for achieving the object of the present invention may further include an additive such as an antifoaming agent, a dispersant, a surface modifier, or an organic solvent for adjusting the curing rate, and does not limit the inclusion of other additives other than these names. . The antifoam may be a silicone-modified polyoxypropylene antifoaming agent, a polyoxyethylene ether dispersant as a dispersant, and a glycidoxypropyltrimethoxysilane-based surface modifier as the surface modifier.

The anticorrosive metal coating composition according to the present invention is used to form a coating layer of a multi-layered structure by forming a separate anticorrosive coating on the top, and the anticorrosive coating film which can be used at this time is not limited to the anticorrosive coating composition including a silane-modified epoxy resin. It is preferable to apply. Non-limiting examples of the anticorrosive coating composition including the silane-modified epoxy resin are disclosed in Korean Patent Publication No. 10-0848671 described in the Background Art.

Method for producing a metal coating composition for corrosion protection according to another aspect of the present invention includes a metal powder dispersion step, the first sol gel resin mixing and stirring step, the second sol gel resin mixing and stirring step.

First, the metal powder dispersion step is a step of mixing 5 to 10㎛ size metal powder in a solvent for 2 to 3 hours at room temperature.

Next, the first sol-gel resin mixing and stirring step is to add the first sol-gel resin to the mixture of the dispersing step and to stir at 300 to 400 rpm for 3 to 5 hours, wherein the temperature is maintained at 15 to 20 ℃ desirable.

Next, the second sol-gel resin mixing and stirring step is a step of adding the second sol-gel resin to the mixture of the above-mentioned first sol-gel resin mixing and stirring step and stirring at 100 to 200 rpm for 4 to 7 hours, wherein the temperature is It is preferable to keep it at 10-15 degreeC.

If it is outside the range of the mixing time, stirring speed, and temperature described above during manufacturing, the sol-gel resin is poor in stability and the anticorrosive period is significantly decreased. For example, when anticorrosive coating of parts such as bolts and nuts using a dipping process, at least six weeks should be used, but a problem arises that only one week can be used.

[Example]

≪ Example 1 >

90 parts by weight of 8 mg aluminum magnesium alloy and 35 parts by weight of 8 um aluminum were mixed with 70 parts by weight of acetone at room temperature for 2 hours, and after adjusting the temperature to 15 ° C., 29 parts by weight of zirconium-tetra-normal-butanolate 15 parts by weight of butoxide and 5 parts by weight of isopropyl titanate were added and stirred at 400 rpm for 5 hours, and then the temperature was reduced to 10 ° C. and the stirring speed was reduced to 100 rpm, respectively, and then tri- (3- (trimethoxysil) propyl) isocytoxy 35 parts by weight of anurate, 60 parts by weight of gamma-methacryloxypropyltrimethoxysilane and 55 parts by weight of normal-phenyl-gamma-aminopropyltrimethoxysilane were added thereto, followed by stirring for 5 hours to prepare an anticorrosive metal coating composition.

At this time, zirconium tatra-normal-butanolate used a molecular weight of 384 (28% zirconium oxide content, 16% normal butanol content), zirconium butoxide has a molecular weight of 383, isopropyl titanate molecular weight of 284 Was used.

Further, tri- (3- (trimethoxysilyl) propyl) isocyanurate has a molecular weight of 136.3, and gamma-methacryloxypropyltrimethoxysilane has a molecular weight of 248.4 and normal-phenyl-gamma-aminopropyltrimethoxy As the silane, a molecular weight of 255.4 was used.

<Example 2>

In Example 1, only 20 parts by weight of zirconium tatra-normal-butanolate was prepared in the same formulation for the anticorrosive metal coating composition.

<Example 3>

In Example 1, only 10 parts by weight of zirconium butoxide was prepared in the same formulation for the anticorrosive metal coating composition.

<Example 4>

Instead of using a mixture of aluminum magnesium alloy and aluminum as the metal powder in Example 1, only 125 parts by weight of aluminum having a size of 8 μm was used.

<Example 5>

Except that the first sol-gel resin and the second sol-gel resin in Example 1 were mixed sequentially and mixed and stirred under the same conditions.

Comparative Example 1

In the same manner as in Example 1, only 15 μm of aluminum magnesium was used.

Comparative Example 2

In Example 1, all were the same and only 20 µm of aluminum magnesium was used.

Comparative Example 3

In Example 1, an epoxy resin was used instead of the sol-gel resin.

[Experimental Example]

Spraying the silane-modified epoxy resin based composition of the Republic of Korea Patent No. 10-0848671 (announced on July 28, 2008) before applying the metal coating composition for corrosion protection prepared in Examples and Comparative Examples on the steel surface before spraying and drying The anticorrosive coating film having a thickness of 20 to 25 μm was formed to measure acid resistance, adhesion, water tightness, corrosion resistance, and metal layer climb phenomenon. All the said anticorrosive coating films were hardened for about 10 minutes at the temperature of 130 degreeC, and were put together as Table 1, and the like.

Properties of the Composite Anticorrosive Coating Layer Evaluation target Assessment Methods Example Comparative Example One 2 3 4 5 One 2 3 Acid resistance No swelling, splitting or peeling after immersion in 10% hydrofluoric acid solution for 30 minutes ◎ ◎ ◎ ○ ○ △ × △ Metal layer climb Visual observation ◎ ○ ◎ ○ △ × △ × Water resistance No swelling, splitting, discoloration or deterioration of adhesion after immersion in water at 40 ± 2 ℃ for 120 hours ◎ ◎ ○ ○ ○ △ × × Corrosion resistance NaCl 5% solution 1000 900 800 800 800 400 300 300 Salt spray test (hours)

 (◎: Very good ○: Good △: Normal ×: Poor)

As shown in Examples 1, 2, and 3 of Table 1, the composite coating composition of the present invention is excellent in acid resistance, water resistance, corrosion resistance, etc., but the anticorrosive coating film coated with the compositions of Comparative Examples 1 and 2 is very poor in all physical properties. appear. This may be due to the size of the aluminum magnesium alloy used as the metal powder, the properties of the sol-gel resin and the ratio of the above-described composition.

Although various embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and those skilled in the art to which the present invention pertains may make modifications without departing from the concept of the present invention. Modifications are within the scope of the present invention.

The scope of the above-described invention is defined in the following claims, not bound by the description in the text of the specification, all modifications and variations belonging to the equivalent scope of the claims will fall within the scope of the invention.

Claims (9)

At least one metal powder having a particle size of 5 to 10 μm and selected from the group consisting of aluminum, magnesium, and alloys thereof;
A first sol-gel resin selected from the group consisting of zirconium tatra-normal-butanolate, zirconium butoxide, isopropyl titanate, and mixtures thereof;
Tri- (3- (trimethoxysil) propyl) isocyanurate, gamma-methacryloxypropyltrimethoxysilane and normal-phenyl-gamma-aminopropyltrimethoxysilane, and mixtures thereof Second sol-gel resin; And
Energy-saving metal coating composition comprising a solvent.

The method of claim 1,
The metal powder is 100 to 160 parts by weight, the first sol-gel resin is 35 to 60 parts by weight, the second sol-gel resin is 165 to 250 parts by weight, the solvent is 60 to 90 parts by weight of the energy-saving metal coating film Composition.

The method of claim 2,
The metal powder is an energy-saving anticorrosive metal coating composition consisting of aluminum magnesium alloy 70 to 100 parts by weight, aluminum 30 to 60 parts by weight.

The method of claim 3,
The first sol-gel resin is composed of 20 to 30 parts by weight of zirconium tatra-normal-butanolate, 10 to 20 parts by weight of zirconium butoxide and 5 to 10 parts by weight of isopropyl titanate. The method of claim 4, wherein
The second sol-gel resin is 30 to 50 parts by weight of tri- (3- (trimethoxysil) propyl) isocyanurate, 50 to 70 parts by weight of gamma-methacryloxypropyltrimethoxysilane and normal-phenyl-gamma- Energy-saving anticorrosive metal coating composition consisting of 50 to 70 parts by weight of aminopropyltrimethoxysilane.

The method of claim 5,
The solvent is acetone energy-saving metal coating composition for anticorrosion.

A metal powder dispersion step of mixing a metal powder selected from the group consisting of aluminum, magnesium, and alloys of 5 to 10 μm in a solvent for 2 to 3 hours;
Zirconium tatra-normal-butanolate, zirconium butoxide, isopropyl titanate, and a first sol gel resin selected from the group consisting of the mixture are added to the mixture of the metal powder dispersion step for 300 to 3 hours. Mixing and stirring the first sol-gel resin, which is stirred at 400 rpm; And
Tri- (3- (trimethoxysil) propyl) isocyanurate, gamma-methacryloxypropyltrimethoxysilane and normal-phenyl-gamma-aminopropyltrime in the mixture of the first sol-gel resin mixing and stirring step Energy-saving anticorrosive metal coating film comprising a; and a second sol-gel resin mixing and stirring step of adding a second sol-gel resin selected from the group consisting of oxysilane, and mixtures thereof and stirring at 100 to 200 rpm for 4 to 7 hours. Method of Preparation of the Composition.

The method of claim 7, wherein
Method for producing an energy-saving anticorrosive metal coating composition to maintain the temperature in the first sol-gel resin mixing and stirring step at 15 to 20 ℃.

The method of claim 8,
Method for producing an energy-saving metal coating composition for the second sol-gel resin mixing and stirring step is maintained at 10 to 15 ℃.